CN103210024A - Prepregs based on a storage-stable reactive or highly reactive polyurethane composition - Google Patents

Prepregs based on a storage-stable reactive or highly reactive polyurethane composition Download PDF

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Publication number
CN103210024A
CN103210024A CN2011800562520A CN201180056252A CN103210024A CN 103210024 A CN103210024 A CN 103210024A CN 2011800562520 A CN2011800562520 A CN 2011800562520A CN 201180056252 A CN201180056252 A CN 201180056252A CN 103210024 A CN103210024 A CN 103210024A
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prepreg
ammonium
polyurethane composition
aforementioned
weight
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Chinese (zh)
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F.G.施密特
S.雷默斯
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Evonik Operations GmbH
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Evonik Degussa GmbH
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/243—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using carbon fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0015—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using fibres of specified chemical or physical nature, e.g. natural silk
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/10—Scrim [e.g., open net or mesh, gauze, loose or open weave or knit, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2926—Coated or impregnated inorganic fiber fabric
    • Y10T442/2984—Coated or impregnated carbon or carbonaceous fiber fabric

Abstract

The invention relates to prepregs based on a storage-stable reactive or highly reactive polyurethane composition for producing composite components with visible carbon fiber woven fabrics or scrims.

Description

Based on the reactivity of stable storing or the prepreg of hyperergy polyurethane composition
The present invention relates to for the manufacture of have visible carbon fibre fabric or-composite component of grid cloth based on the reactivity of stable storing or the prepreg of hyperergy polyurethane composition.
Prior art
Known to the reactivity of stable storing or the prepreg of hyperergy polyurethane composition from DE 102009001793, DE 102009001806 and DE 10201029355.
Fibre composite is processed as the design object more and more continually.
As seen the outward appearance of the noble quality of carbon fibre fabric especially is used in the motor vehicle structure, particularly in motor sport and in the model construction.In addition, this matrix material (profiled member) has high structural load ability, has also realized high physical strength thus.
The fibrous texture that term " visible carbon ", " carbon fabric visible structure ", " carbon outward appearance " and " carbon appearance " are understood to mean in matrix material (parts), sheet material and film carbon fibre fabric or grid cloth is visible, sees figure A, carbon fibre fabric.
Usually must process composite component (laminating material and/or sandwich component) to improve or to promote surface quality or the image appearance (Sichtbarmachung) of carbon fibre fabric or carbon fiber mesh fabric.Usually, be coated with this goods with varnish or with transparent plastics.
Directly make corresponding composite component by so-called prepreg technology and be still problem to be solved so far.
The objective of the invention is can be enough based on the reactivity of stable storing or the visible carbon composite component of special prepreg manufacturing of hyperergy polyurethane composition.
Use based on the reactivity of the stable storing that when making prepreg, has been contained in the fiber volume fraction with obvious reduction in the substrate material composition or the prepreg of hyperergy aliphatic urethane composition and realize described purpose.
Have been found that, by using the special prepreg based on aliphatic urethane matrix can make the fast light composite component with A level surface, described prepreg had by used and the visible that becomes reduction fiber volume fraction carbon fiber-fabric or-grid cloth makes.
Theme of the present invention is the prepreg that has less than 50% fiber volume fraction, and it is following formation basically
A) at least a fibrous carrier that is constituted by carbon fiber
With
B) at least a reactivity or hyperergy transparent polyurethane composition be as substrate material,
Wherein said polyurethane composition contains the polymkeric substance b with isocyanate-reactive functional group as tackiness agent basically) and as the inside end-blocking of solidifying agent and/or with the aliphatic series of end-capping reagent end-blocking, alicyclic and/or (ring) aliphatic series two-or polyisocyanates mixture a).
This transparent matrix material can comprise suitable photostabilizer and/or oxidation stabilizer in addition.
Have with used fibrous carrier A according to prepreg of the present invention with by its matrix material of making (parts)) the surface of visible structure.
Can implement the manufacturing of prepreg in principle by any means.
With suitable manner, by powder impregnation, preferably will be according to Powdered reactivity of the present invention or hyperergy polyurethane composition B by powder injection process) be applied on the carrier.Fluidized-bed sintering process, pultrusion or spraying method are also feasible.Preferably by powder injection process powder (a whole or part) is applied on the fibrous carrier, for example is applied on the band of carbon fiber mesh fabric (Gelege) or fabric, fixing then.For avoiding the powder loss, the preferred fibrous carrier that loads with powder that directly will be somebody's turn to do after the program of dusting (is for example used the IR radiator) and is heated in heating zone, so that the particle sintering should not surpass 80 to 100 ℃ temperature, to prevent the reaction of hyperergy substrate material in this process.These prepregs can make up and cut into multi-form on demand.
Also can implement the manufacturing of prepreg according to direct melt impregnation method.The direct melt impregnation ratio juris of prepreg is, is at first made in melt according to Powdered reactivity of the present invention or hyperergy polyurethane composition B by its each component).Then will be according to Powdered reactive polyurethane composition B of the present invention) this melt be applied directly to fibrous carrier A) on, in other words use B) melt carry out fibrous carrier A) dipping.After this, can further be processed into matrix material at the stored prepreg that the time after a while will cool off.By direct melt impregnation method according to the present invention, because this liquid hangs down the fiber of the sticking fabulous wetting carrier of reactive polyurethane composition, cause the fabulous dipping of fibrous carrier.
Also can use solvent to carry out the manufacturing of prepreg.This prepreg is made ratio juris and is thereupon, is at first made according to reactivity of the present invention or hyperergy polyurethane composition B by its each component in suitable common solvent) solution or dispersion.Then with reactive polyurethane composition B) this solution or dispersion be applied directly to fibrous carrier A) on, this fibrous carrier is soaked into/floods by this solution thus.Subsequently, desolventizing.Preferably by for example thermal treatment or apply vacuum at low temperature, preferred＜100 ℃ of complete desolventizings down.After this, this stored prepreg that can will remove solvent in the time after a while more further is processed into matrix material.By method of the present invention, because the fiber of the fabulous wetting carrier of solution of this reactive polyurethane composition, cause the fabulous dipping of fibrous carrier.
As the solvent that is applicable to method of the present invention, can use not with the reactive polyurethane composition react, each component of used reactive polyurethane composition is had enough dissolving poweies and can remove all aprotic liquids up to small trace (＜0.5 weight %) in solvent removal processing step process from the prepreg that soaks into the reactive polyurethane composition, wherein the recirculation of the solvent of Fen Liing is favourable.
For example, can mention at this: ketone (acetone, methylethylketone, methyl iso-butyl ketone (MIBK), pimelinketone), ether (tetrahydrofuran (THF)), ester (n-propyl acetate, n-butyl acetate, isobutyl acetate, carbonic acid-1,2-Isopropanediol ester, propylene glycol methyl ether acetate).
After being cooled to room temperature, prepreg according to the present invention has high stability in storage at room temperature, as long as substrate material has at least 40 ℃ Tg.According to contained reactive polyurethane composition, this is at room temperature at least several days, but this prepreg is usually 40 ℃ and stable storing several weeks under the low temperature more.The prepreg of making thus is not also therefore very easy operation and the further processing of thickness.Therefore reactivity used according to the invention or hyperergy polyurethane composition show fabulous on fibrous carrier and adhere to and distribute.
Further be processed in the process of matrix material (for example by compacting at elevated temperatures) at prepreg, taking place by reactivity or hyperergy polyurethane composition crosslinking reaction at elevated temperatures before gelling or whole polyurethane substrates solidify fully, owing to should liquid state hang down the fiber that glues reactivity or hyperergy polyurethane composition fabulous wetting carrier before crosslinking reaction in this case, cause the fabulous dipping of fibrous carrier.
Can be on demand with the prepreg combination of so making with cut into multi-form.
For prepreg being merged into single matrix material and for making substrate material be cross-linked into matrix, cutting prepreg, optional sew up or fixing and in suitable mould, suppress at pressure and optional applying under the vacuum in addition.Within the scope of the present invention, according to set time, when using reactive substrate material (scheme I) in the operation of under the temperature more than 100 ℃, carrying out being made by prepreg matrix material under about temperature more than 160 ℃ or when use has the hyperergy substrate material (scheme II) of appropriate catalyst.
Composition and the optional catalyzer that adds according to used reactivity or hyperergy polyurethane composition can change the speed of the crosslinking reaction in the composite component manufacturing and the character of matrix in wide region.
As substrate material, within the scope of the present invention, be defined as for the manufacture of reactivity or the hyperergy polyurethane composition of prepreg and in the description of prepreg, be defined as being applied to the polyurethane composition that also has reactivity or hyperergy on the fiber by method of the present invention.
Matrix is defined in the crosslinked substrate material that is made of reactivity or hyperergy polyurethane composition in this matrix material.
Carrier
Described fibrous carrier is made of fibrous material (being also referred to as fortifying fibre usually) in the present invention.Usually, any material of formation carbon fiber all is suitable.Carbon fiber (being also referred to as carbon fiber) is by containing the industrial fiber that carbon source materials is made, and it changes into the carbon of graphite-like structure by pyrolysis.Distinguish isotropy and anisotropy type: isotropic fiber only has low strength and low industrial significance, and the anisotropy fiber shows high strength and the simultaneously little extension at break of rigidity.
This fibrous material is planar textile structures.The spinning plane configuration articles of supatex fabric, and so-called knitted fabrics, as tricot and weft-knitted fabric (Gestricke), and non-knitting thread yarn (Gebinde), be suitable as fabric (Gewebe), grid cloth or cloth (Geflechte).In addition, distinguish macrofiber-and short fiber material as carrier.All described materials all are suitable as the fibrous carrier in the scope of the invention.The summary that in " Composites Technologien, Paolo Ermanni (the 4th edition), Script zur Vorlesung ETH Z ü rich, in August, 2007, the 7th chapter ", comprises strongthener.
Preferably use fabric and the grid cloth of carbon fiber as carrier.
According to the present invention, the fiber volume fraction of this prepreg is＜50%, and preferred＜40% more preferably＜35% does not wait.
Substrate material
In principle, the reactivity of all fast light stable storings at room temperature or hyperergy transparent polyurethane composition are suitable as substrate material.According to the present invention, suitable polyurethane composition by have can with the polymkeric substance b of the functional group of NCO radical reaction) (tackiness agent), be also referred to as resin and temporary transient inactivation, in other words inner end-blocking and/or with the aliphatic series of end-capping reagent end-blocking, alicyclic and/or (ring) aliphatic series two-or polyisocyanates, be also referred to as solidifying agent a) mixture of (component a)) constitute
As polymkeric substance b) functional group of (tackiness agent), hydroxyl, amino and thiol group are suitable, they and free isocyanate groups group's addition reaction and crosslinked and curing urethane composition thus.This binder ingredients must have solid resin character (second-order transition temperature is higher than room temperature).As tackiness agent suitable be that to have the OH value be that 20 to 500 milligrams of KOH/ gram and average molar mass are polyester, polyethers, polyacrylic ester, polycarbonate and the urethane of 250 to 6000 grams/mole.Especially preferably having the OH value is that 20 to 150 milligrams of KOH/ grams and molecular-weight average are polyester or the polyacrylic ester of the hydroxyl of 500 to 6000 grams/mole.Certainly, also can use such mixture of polymers.So select to have the polymkeric substance b of described functional group) to such an extent as to amount in components b) each functional group consume component 0.6 to 2 NCO equivalent or 0.3 to 1 uretdion groups a).
As curing agent component a), use by two of the end-blocking end-capping reagent end-blocking or inner (urea diketone)-and polyisocyanates.
Used according to the invention two-and polyisocyanates can be by any aromatics, aliphatic series, alicyclic and/or (ring) aliphatic series two-and/or polyisocyanates formation.
Suitable aliphatic series two-or polyisocyanates advantageously in the straight or branched alkylidene residue, have 3 to 16 carbon atoms, preferred 4 to 12 carbon atoms, and suitable alicyclic or (ring) aliphatic vulcabond advantageously has 4 to 18 carbon atoms, preferred 6 to 15 carbon atoms in the ring alkylidene residue.(ring) aliphatic vulcabond is fully understood NCO group into while ring-type and aliphatic bonding, situation about for example coming to this by those skilled in the art in isophorone diisocyanate.On the contrary, alicyclic diisocyanate is understood to mean those that only have the NCO group that is bonded directly on the alicyclic ring, for example H 12MDI.Example is cyclohexyl diisocyanate, methylcyclohexane diisocyanate, the ethylcyclohexane vulcabond, the propyl cyclohexane vulcabond, methyl diethyl cyclohexane vulcabond, the propane vulcabond, the butane vulcabond, the pentane vulcabond, hexane diisocyanate, the heptane vulcabond, the octane vulcabond, the nonane vulcabond, nonane triisocyanate, as 4-isocyanato-methyl isophthalic acid, 8-octane vulcabond (TIN), decane two-and triisocyanate, undecane two-and-triisocyanate and dodecane two-and-triisocyanate.
Preferred isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), two isocyanato-dicyclohexyl methyl hydride (H 12MDI), 2-methylpentane vulcabond (MPDI), 2,2,4-trimethyl hexamethylene diisocyanate/2,4,4-trimethyl hexamethylene diisocyanate (TMDI), norbornene alkyl diisocyanate (NBDI).Very particularly preferably use IPDI, HDI, TMDI and/or H 12MDI wherein also can use isocyanuric acid ester.4-methyl-cyclohexyl alkane-1,3-vulcabond, 2-butyl-2-ethyl penta methylene diisocyanate, 3 (4)-isocyanato-methyl isophthalic acid-isocyanatomethyl, 2-isocyanato-propyl group cyclohexyl isocyanate, 2,4 ' methylene-bis (cyclohexyl) vulcabond, 1,4-two isocyanato-s-4-methyl-pentane is also suitable.
Certainly, also can use two-and the mixture of polyisocyanates.
In addition, preferred use can by described two-or polyisocyanates or its mixture by with carbamate-, allophanate-, urea-, biuret-, the urea diketone-, acid amides-, isocyanuric acid ester-, carbodiimide-, uretonimine-, oxadiazine triketones-or the oligomeric or polyisocyanates made of iminooxadiazinedionepolyisocyanates diketone structure connection.Specially suitable is isocyanuric acid ester, particularly derives from IPDI and HDI.
Polyisocyanates used according to the invention is end-blocking.Outside end-capping reagent, for example methyl aceto acetate, Diisopropylamine, methyl ethyl ketone oxime, diethyl malonate, ε-Ji Neixianan, 1,2,4-triazole, phenol or substituted phenol and 3 can be used for this.
The preferred curing agent component that uses is the IPDI adducts that contains the isocyanic ester structure of isocyanurate group and ε-Ji Neixianan end-blocking.
The also feasible and preferred use of inner end-blocking.Realize inner end-blocking by forming dimer via the urea diketone structure, described urea diketone structure at elevated temperatures again cracking become the isocyanic ester structure of initial existence and therefore begin with tackiness agent crosslinked.
Randomly, this reactive polyurethane composition can contain other catalyzer.These are organo-metallic catalysts of the amount of 0.001-1 weight %, for example dibutyl tin laurate (DBTL), stannous octoate, neodecanoic acid bismuth or tertiary amine, for example 1,4-diazabicyclo [2.2.2]-octane.These reactive polyurethane compositions used according to the invention are for example used DBTL catalysis under normal operation, from 160 ℃, solidify and be known as scheme I from about 180 ℃ usually.
In order to make the reactive polyurethane composition, can add common additive in the powder coating technology with the total amount of 0.05 to 5 weight %, as flow agent; for example poly organic silicon or acrylate; bright protective agent, for example bulky amine, or other additive as describing among the EP 669 353.
Within the scope of the present invention, reactive (scheme I) refers to reactive polyurethane composition used according to the invention as mentioned above under 160 ℃ temperature, and solidifies according to the character of carrier.
The reactive polyurethane composition that the present invention uses solidifies under normal operation, for example uses DBTL catalysis, from 160 ℃, usually from about 180 ℃ of curing.The time that polyurethane composition used according to the invention is used for solidifying is usually in 5 to 60 minutes.
Preferably use by the polyurethane composition B that contains reactive uretdion groups in the present invention) the substrate material B that makes), it contains basically
A) at least a solidifying agent that contains uretdion groups, polyaddition compounds based on the compound of the aliphatic or alicyclic polyisocyanates that contains uretdion groups of aliphatic series, (ring) and hydroxyl, wherein this solidifying agent exists with solid form below 40 ℃ and exists with liquid form more than 125 ℃, and have less than the free NCO content of 5 weight % and the urea diketone content of 3-25 weight %
B) polymkeric substance of at least a hydroxyl, it exists with solid form below 40 ℃ and exists with liquid form more than 125 ℃, and has 20 to 200 milligrams of OH values between the KOH/ gram,
C) optional at least a catalyzer,
D) randomly, by polyurethane chemistry known auxiliary agent and additive,
So that these two kinds of components a) and b) exist with following ratio, namely in components b) each hydroxyl consume a) 0.3 to 1 of component, preferred 0.45 to 0.55 uretdion groups.The latter is equivalent to 0.9 to 1.1 to 1 NCO/OH ratio.
The polyisocyanates that contains uretdion groups is known and for example is described in US 4,476,054, among US 4,912,210, US 4,929,724 and the EP 417 603.In J. Prakt. Chem. 336 (1994) 185-200, provide the comprehensive review that generates the industrial methods involving of urea diketone about the isocyanic ester dimerization.Usually, what isocyanic ester generated the urea diketone is reflected at solubility dimerization catalyzer, and for example dialkyl amino yl pyridines, trialkyl phosphine, tricresyl phosphite acid amides or imidazoles carry out under existing.Described reaction is chosen wantonly in solvent, but preferably carries out under the situation that does not have solvent, is realizing that desirable conversion back stops this reaction by adding catalyzer poison.Remove excessive monomeric diisocyanate by short-path distillation then.If this catalyzer volatility is enough, then can in removing the process of monomer, from reaction mixture, remove catalyzer.Can abandon adding catalyzer poison in this case.In principle, multiple isocyanic ester is applicable to and makes the polyisocyanates that contains uretdion groups.Can use above-mentioned two-and polyisocyanates.But, preferably arbitrarily aliphatic, alicyclic and/or (ring) aliphatic two-and/or two-and polyisocyanates of polyisocyanates.Isophorone diisocyanate used according to the invention (IPDI), hexamethylene diisocyanate (HDI), two isocyanato-dicyclohexyl methyl hydride (H 12MDI), 2-methylpentane vulcabond (MPDI), 2,2,4-trimethyl hexamethylene diisocyanate/2,4,4-trimethyl hexamethylene diisocyanate (TMDI), norbornene alkyl diisocyanate (NBDI).Very particularly preferably use IPDI, HDI, TMDI and/or H 12MDI wherein also can use isocyanuric acid ester.
Very particularly preferably use IPDI and/or HDI to be used for described substrate material.These polyisocyanates that contain uretdion groups generate solidifying agent reaction a) contain uretdion groups and comprise free NCO group and monomer or polymkeric substance as the hydroxyl of chain extension agent, for example polyester, polythioether, polyethers, polycaprolactam, polyepoxide, polyesteramide, urethane or lower molecular weight two-, three-and/or the reaction of tetravalent alcohol and optional monoamine and/or monohydroxy-alcohol as chain terminator, and often be described (EP 669 353, EP 669 354, DE 30 30 572, EP 639 598 or EP 803 524).
The solidifying agent that preferably has a uretdion groups a) has free NCO content and 3 to 25 weight % less than 5 weight %, and the uretdion mass contg of preferred 6 to 18 weight % is (as C 2N 2O 2Calculate molecular weight 84).Polyester and monomer dibasic alcohol are preferred.Except uretdion groups, this solidifying agent also can have isocyanuric acid ester-, biuret-, allophanate-, carbamate-and/or urea-structure.
Polymkeric substance b for hydroxyl), the preferred use has polyester, polyethers, polyacrylic ester, urethane and/or the polycarbonate that the OH value is 200 milligrams of KOH/ grams of 20 –.Preferred especially the use exists with solid form below 40 ℃ and is being 30-150 in the OH value that has that exists with liquid form more than 125 ℃, molecular-weight average be 500-6000 grams/mole polyester.Such tackiness agent for example has been described among the EP 669 354 and EP 254 152.Certainly, also can use such mixture of polymers.So select the polymkeric substance b of hydroxyl) amount, to such an extent as in components b) each hydroxyl consume component a) 0.3 to 1, preferred 0.45 to 0.55 uretdion groups.Randomly, at reactive polyurethane composition B of the present invention) in can contain other catalyzer c).These are organo-metallic catalysts of the amount of 0.001-1 weight %, for example dibutyl tin laurate, zinc octoate, neodecanoic acid bismuth or tertiary amine, for example 1,4-diazabicyclo [2.2.2] octane.These reactive polyurethane compositions used according to the invention are for example used DBTL catalysis under normal operation, from 160 ℃, solidify and be known as scheme I from about 180 ℃ usually.
In order to make reactive polyurethane composition of the present invention; can add common additive such as flow agent in the powder coating technology with the total amount of 0.05 to 5 weight %; for example poly organic silicon or acrylate; bright protective agent; bulky amine for example, oxidation stabilizer or other auxiliary agent of for example in EP 669 353, describing.
As oxidation stabilizer suitable for example be the phenol antioxidant that contains at least one hindered phenolic group.The example of these phenol antioxidant is: 2,6-two-tertiary butyl-4-methylphenol, 2,4,6-three-tert.-butyl phenol, 2,2 '-methylene-bis (4-methyl-6-tert butyl phenol), 2,2 '-thiobis (4-methyl-6-tert butyl phenol), 4,4 '-thiobis (3 methy 6 tert butyl phenol), 4,4 '-butylidene-bis(3-methyl-6-t-butyl phenol), 4,4 '-methylene-bis (2,6-two-tert.-butyl phenol), 2,2 '-methylene-bis [4-methyl-6-(1-methylcyclohexyl) phenol], four [methylene radical-3-(3,5-two-tertiary butyl-4-hydroxyphenyl) propionic ester] methane, 1,3,5-trimethylammonium-2,4,6-three (3,5-two-tertiary butyl-4-hydroxy benzyl) benzene, N, N '-hexa-methylene two (3,5-, two-tertiary butyl-4-hydroxy hydrocinnamamide), 3-(3,5-, two-tert-butyl-hydroxy phenyl) propionic acid stearyl, 1,3,5-three-(3,5-, two-tertiary butyl-4-hydroxy benzyl) isocyanuric acid ester, 1,1,3-three-(5-tertiary butyl-4-hydroxy-2-aminomethyl phenyl) butane, 1,3,5-three-(3,5-, two-tertiary butyl-4-hydroxy benzyl) sym-trimethylbenzene; Ethylene glycol bis [3,3-pair (3 '-tertiary butyl-4 '-hydroxy phenyl) butyric ester], 2,2 '-the sulfo-diethyl is two-3-(3,5-two-tert-butyl-hydroxy phenyl) propionic ester, 2,2 '-methylene-bis(4-methyl-6-cyclohexyl phenol), 1,6-hexylene glycol-two (3,5-two-tert-butyl-hydroxy phenyl) propionic ester, 2, two (n-octyl sulfo-)-6-(the 4-hydroxyls-3 of 4-, 5-two-tert.-butylbenzene amido)-1,3,5-triazine, 3,5-, two-tertiary butyl-4-hydroxy-benzylphosphonic acid diethyl ester and triethylene glycol-two-3-(tertiary butyl-4-hydroxy-5-aminomethyl phenyl)-propionic ester.
Same suitable be stablizer, P contained compound for example, three esters of preferred phosphorous acid, for example trialkyl phosphite and triaryl phosphites, and thioether.
Photostabilizer is known and for example is described in detail at Hans Zweifel, Plastics Additives Handbook, Hanser Verlag, the 5th edition, 2001, the 141 pages and with in the last few pages.Photostabilizer should be understood to mean UV light absorber, ultra-violet stabilizer and free radical scavenger.
UV light absorber can for example be derived from substituted benzophenone, salicylate, laurate, oxanilide, benzoxazinone, hydroxy phenyl benzotriazole, triazine or benzylidene malonate.
Also can use the UV light absorber of benzotriazole type.These UV light absorber are for example sold (2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole) by Ciba Specialty Chemicals Inc. with Tinuvin P trade mark).
The known representative of ultra-violet stabilizer/free radical scavenger be the steric hindrance amine (hindered amine as light stabilizer, HALS).These are derivatives of 2,2,6,6-tetramethyl piperidine, for example triacetonamine (Triazetonamin) (2,2,6,6-tetramethyl--4-piperidone).
Reactive polyurethane composition used according to the invention is for example used DBTL catalysis under normal operation, from 160 ℃, usually from about 180 ℃ of curing.Reactive polyurethane composition used according to the invention provide excellent flowing and therefore good dipping ability and under solid state excellent chemical resistance.In addition, using aliphatic linking agent (for example IPDI or H 12MDI) time, also realize good weathering resistance in addition.
The substrate material that preferred especially use is in the present invention made by following material
B) at least a hyperergy polyurethane composition that contains uretdion groups, it contains basically
A) at least a solidifying agent that contains uretdion groups, it is based on aliphatic or alicyclic two of uretdion groups-or the polyisocyanates that contains of aliphatic series, (ring),
With
B) optional at least a polymkeric substance with NCO radical reaction functional group;
C) at least a catalyzer of 0.1 to 5 weight %, it is selected from halogen ion, hydroxide radical, alcoholate ion or organic or inorganic acid anion is quaternary ammonium salt and/or the quaternary alkylphosphonium salt of counter ion;
With
D) at least a promotor of 0.1 to 5 weight %, it is selected from
D1) at least a epoxide
And/or
D2) at least a metal acetylacetonates and/or quaternary ammonium acetylacetonate and/or quaternary phosphine acetylacetonate; With
E) randomly, by polyurethane chemistry known auxiliary agent and additive.
The very special substrate material B that is made by following material that uses)
B) at least a Powdered polyurethane composition of hyperergy that contains uretdion groups is as substrate material, and it contains basically
A) at least a solidifying agent that contains uretdion groups, described solidifying agent is based on the polyaddition compounds of the compound of the aliphatic or alicyclic polyisocyanates that contains uretdion groups of aliphatic series, (ring) and hydroxyl, wherein this solidifying agent exists with solid form below 40 ℃ and exists with liquid form more than 125 ℃ and have less than the free NCO content of 5 weight % and the urea diketone content of 3-25 weight %
B) polymkeric substance of at least a hydroxyl, it exists with solid form below 40 ℃ and exists with liquid form more than 125 ℃ and have 20 to 200 milligrams of OH values between the KOH/ gram;
C) at least a catalyzer of 0.1 to 5 weight %, it is selected from halogen ion, hydroxide radical, alcoholate ion or organic or inorganic acid anion is quaternary ammonium salt and/or the quaternary alkylphosphonium salt of counter ion;
With
D) at least a promotor of 0.1 to 5 weight %, it is selected from
D1) at least a epoxide
And/or
D2) at least a metal acetylacetonates and/or quaternary ammonium acetylacetonate and/or quaternary phosphine acetylacetonate; With
E) randomly, by polyurethane chemistry known auxiliary agent and additive,
So that these two kinds of components a) and b) exist with following ratio, namely in components b) each hydroxyl consume a) 0.3 to 1 of component, preferred 0.6 to 0.9 uretdion groups.The latter is equivalent to the NCO/OH ratio of 0.6-2:1 or 1.2-1.8:1.These hyperergy polyurethane compositions used according to the invention solidify under 100 to 160 ℃ temperature and are known as scheme II.
According to the present invention, the suitable hyperergy polyurethane composition that contains uretdion groups contains the mixture of following component: temporary transient inactivation, namely contain (the inner end-blocking) two of uretdion groups-or polyisocyanates, be also referred to as solidifying agent a), with the catalyzer c that comprises according to the present invention) and d) and the optional polymkeric substance (tackiness agent) that has NCO radical reaction functional group in addition, be also referred to as resin b).Catalyzer guarantees that the polyurethane composition that contains uretdion groups solidifies at low temperatures.Therefore this polyurethane composition that contains uretdion groups is hyperergy.
As component a) and b), use as described above those.
As c) under catalyzer, use with halogen ion, hydroxide radical, alcoholate ion or the organic or inorganic acid anion quaternary ammonium salt as counter ion preferred tetraalkylammonium salt and/or quaternary alkylphosphonium salt.These example is: the tetramethyl-ammonium formiate, tetramethyl ammonium acetate, tetramethyl-propionic acid ammonium, tetramethyl-butyric acid ammonium, the tetramethyl-benzene ammonium formiate, the tetraethyl-ammonium formiate, the tetraethyl-ammonium acetate, tetraethyl-propionic acid ammonium, tetraethyl-butyric acid ammonium, the tetraethylbenzene ammonium formiate, the tetrapropyl ammonium formiate, the tetrapropyl ammonium acetate, tetrapropyl propionic acid ammonium, tetrapropyl butyric acid ammonium, the tetrapropyl ammonium benzoate, tetrabutyl ammonium formiate, tetrabutyl ammonium acetate, tetrabutyl propionic acid ammonium, tetrabutyl butyric acid ammonium and tetrabutyl ammonium benzoate and tetrabutyl Yi Suan Phosphonium, tetrabutyl Jia Suan Phosphonium and ethyl triphenyl Yi Suan Phosphonium, 4-butyl-phosphonium benzotriazole salt, tetraphenyl phosphonium phenolates and three hexyl tetradecyl Gui Suan Phosphonium, methyl tributyl ammonium hydroxide, methyl triethyl ammonium hydroxide, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH, TBAH, four pentyl ammonium hydroxide, four hexyl ammonium hydroxide, four octyl group ammonium hydroxide, four decyl ammonium hydroxide, tetradecyl three hexyl ammonium hydroxide, four-octadecyl ammonium hydroxide, benzyltrimethylammonium hydroxide, benzyl triethyl ammonium ammonium hydroxide, trimethylphenyl ammonium hydroxide, the triethyl ammonium hydroxide, neurine, the methyl tributyl methanol ammonium hydroxide, methyl triethyl-carbinol ammonium, the tetramethyl-methanol ammonium hydroxide, the tetraethyl-methanol ammonium hydroxide, the tetrapropyl methanol ammonium hydroxide, tetrabutyl methanol ammonium hydroxide, the four pentyl methanol ammonium hydroxide, four hexyl methanol ammonium hydroxides, four octyl carbinol ammoniums, four decyl methanol ammonium hydroxides, tetradecyl three hexyl methanol ammonium hydroxides, four-octadecyl methanol ammonium hydroxide, the benzyl trimethyl methanol ammonium hydroxide, the benzyl triethyl ammonium methanol ammonium hydroxide, the trimethylphenyl methanol ammonium hydroxide, triethyl carbinol methine ammonium, trimethyl-ethylene base methanol ammonium hydroxide, methyl tributyl ethanol ammonium, methyl triethyl ethanol ammonium, tetramethyl-ethanol ammonium, tetraethyl-ethanol ammonium, tetrapropyl ethanol ammonium, tetrabutyl ethanol ammonium, four pentyl ethanol ammonium, four hexyl ethanol ammoniums, four octyl carbinol ammoniums, four decyl ethanol ammoniums, tetradecyl three hexyl ethanol ammoniums, four-octadecyl ethanol ammonium, benzyl trimethyl ethanol ammonium, benzyl triethyl ammonium ethanol ammonium, trimethylphenyl ethanol ammonium, triethyl methyl ethanol ammonium, trimethyl-ethylene base ethanol ammonium, methyl tributyl benzylalcohol ammonium, methyl triethyl benzylalcohol ammonium, tetramethyl-benzylalcohol ammonium, tetraethyl-benzylalcohol ammonium, tetrapropyl benzylalcohol ammonium, tetrabutyl benzylalcohol ammonium, four pentyl benzylalcohol ammonium, four hexyl benzylalcohol ammoniums, four octyl group benzylalcohol ammoniums, four decyl benzylalcohol ammoniums, tetradecyl three hexyl benzylalcohol ammoniums, four-octadecyl benzylalcohol ammonium, benzyl trimethyl benzylalcohol ammonium, benzyl triethyl ammonium benzylalcohol ammonium, trimethylphenyl benzylalcohol ammonium, triethyl xylyl alcohol ammonium, trimethyl-ethylene base benzylalcohol ammonium, Methanaminium, N,N,N-trimethyl-, fluoride, tetraethyl ammonium fluoride, tetrabutyl ammonium fluoride, four octyl group Neutral ammonium fluorides, the benzyl trimethyl Neutral ammonium fluoride, Si butyl phosphonium hydroxides, four butyl are fluoridized Phosphonium, tetrabutylammonium chloride, Tetrabutyl amonium bromide, tetrabutylammonium iodide, etamon chloride, tetraethylammonium bromide, tetraethyl ammonium iodide, tetramethyl ammonium chloride, 4 bromide, Tetramethylammonium iodide, benzyl trimethyl ammonium chloride, benzyltriethylammoinium chloride, benzyl tripropyl ammonium chloride, benzyl tributyl ammonium chloride, methyltributylammonichloride chloride, methyl tripropyl ammonium chloride, the methyl triethyl ammonium chloride, methyl triphenyl ammonium chloride, the phenyl trimethyl ammonium chloride, benzyltrimethylammonium bromide, benzyl triethyl ammonium bromide, benzyl tripropyl brometo de amonio, benzyl tributyl brometo de amonio, the methyl tributyl brometo de amonio, methyl tripropyl brometo de amonio, methyl triethyl brometo de amonio, the methyltriphenylphospbromide bromide ammonium, the phenyl trimethylammonium bromide, benzyltrimethylammonium iodide, the benzyl triethyl ammonium ammonium iodide, benzyl tripropyl ammonium iodide, benzyl tributyl ammonium iodide, the methyl tributyl ammonium iodide, methyl tripropyl ammonium iodide, methyl triethyl iodate ammonium, methyl triphenyl ammonium iodide and phenyl trimethylammonium ammonium iodide, methyl tributyl ammonium hydroxide, methyl triethyl ammonium hydroxide, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH, TBAH, four pentyl ammonium hydroxide, four hexyl ammonium hydroxide, four octyl group ammonium hydroxide, four decyl ammonium hydroxide, tetradecyl three hexyl ammonium hydroxide, four-octadecyl ammonium hydroxide, benzyltrimethylammonium hydroxide, benzyl triethyl ammonium ammonium hydroxide, trimethylphenyl ammonium hydroxide, the triethyl ammonium hydroxide, neurine, Methanaminium, N,N,N-trimethyl-, fluoride, tetraethyl ammonium fluoride, tetrabutyl ammonium fluoride, four octyl group Neutral ammonium fluorides and benzyl trimethyl Neutral ammonium fluoride.These catalyzer can add individually or with mixture.Preferred tetraethylbenzene ammonium formiate and/or the TBAH used.
Catalyzer c) content can be 0.1 to 5 weight %, and preferred 0.3 to 2 weight % is based on total preparation meter of this substrate material.
A scheme according to the present invention comprises such catalyzer c) be bonded to polymkeric substance b) functional group on.In addition, these catalyzer can be surrounded also packing thus by the inertia shell.
As promotor d1), use epoxide.At this suitable be for example glycidyl ether and glycidyl ester, aliphatic epoxide, based on diglycidylether and the glycidyl methacrylate of dihydroxyphenyl propane.The example of such epoxide is triglycidyl isocyanurate (TGIC, trade(brand)name Araldit 810, Huntsman), the mixture of terephthalic acid diglycidyl ester and trimellitic acid three-glycidyl ester (trade(brand)name Araldit PT 910 and 912, Huntsman), the glycidyl ester of Versatic acid (trade(brand)name Kardura E10, Shell), 3,4-epoxycyclohexyl methyl-3 ', 4 '-epoxy cyclohexane manthanoate (ECC), (trade(brand)name EPIKOTE 828 based on the diglycidylether of dihydroxyphenyl propane, Shell), the ethylhexyl glycidyl ether, butylglycidyl ether, tetramethylolmethane four glycidyl ethers (trade(brand)name Polypox R 16, UPPC AG) and have other Polypox type of free epoxy group(ing).Also can use mixture.The preferred ARALDIT PT 910 and 912 that uses.
As promotor d2), suitable is metal acetylacetonates.These example is zinc acetylacetonate, acetylacetonate lithium and acetylacetonate tin independent or that mix.The preferred zinc acetylacetonate of using.
As promotor d2), suitable is quaternary ammonium acetylacetonate Huo quaternary phosphine acetylacetonate in addition.
The example of such catalyzer is tetramethyl-acetylacetonate ammonium, tetraethyl-acetylacetonate ammonium, tetrapropyl acetylacetonate ammonium, tetrabutyl acetylacetonate ammonium, benzyl trimethyl acetylacetonate ammonium, benzyl triethyl ammonium acetylacetonate ammonium, tetramethyl ethylacetoacetone Phosphonium, tetrem ethylacetoacetone Phosphonium, the tetrapropyl second acyl third ketone Phosphonium, the tetrabutyl second acyl third ketone Phosphonium, the benzyl trimethyl second acyl third ketone Phosphonium and the benzyl triethyl ammonium second acyl third ketone Phosphonium.Especially preferably use tetraethyl-acetylacetonate ammonium and/or tetrabutyl acetylacetonate ammonium.Can certainly use these mixture of catalysts.
Promotor d1) and/or content d2) can be 0.1 to 5 weight %, preferred 0.3 to 2 weight % is based on total preparation meter of this substrate material.In order to make according to hyperergy polyurethane composition of the present invention; can be as mentioned above; total amount with 0.05 to 5 weight % is added common additive in the powder coating technology; as flow agent; for example poly organic silicon or acrylate; bright protective agent, for example bulky amine, oxidation stabilizer or other additive of for example in EP 669 353, describing.
By means of hyperergy used according to the invention and so low-temperature curing polyurethane composition B), under 100 to 160 ℃ of solidification values, not only can save energy and set time, can also use many temperature sensitive carriers.
Within the scope of the present invention, hyperergy (scheme II) refers to that the polyurethane composition that contains uretdion groups used according to the invention solidifies under 100 to 160 ℃ temperature and according to the character of carrier.This solidification value is preferably 120 to 150 ℃, preferred especially 130 to 140 ℃.The set time of polyurethane composition used according to the invention is in 5 to 60 minutes.
The reactivity that contains uretdion groups used according to the invention or hyperergy polyurethane composition B) provide excellent flowing and therefore good dipping ability and under solid state excellent chemical resistance.In addition, using aliphatic linking agent (for example IPDI or H 12MDI) time, also realize good weathering resistance in addition.
The manufacturing of described substrate material can followingly be carried out: for the manufacture of polyurethane composition B) the homogenizing of all components can be at suitable device, for example heatable stirring tank, kneader or even forcing machine in carry out, in this process, should not surpass 120 to 130 ℃ upper temperature limit.The mixing of each component is preferably being carried out under the following temperature in forcing machine: although this temperature is positioned at more than the fusion range of each component, be positioned at below the temperature of beginning crosslinking reaction.After this can directly be used by melt or use in cooling and the back that makes powder.Also can be in solvent carry out polyurethane composition B by in aforementioned means, mixing) manufacturing.
Then, according to method, with substrate material B) with carrier A) be processed into prepreg.
Reactivity or hyperergy polyurethane composition according to the present invention as substrate material are made of the mixture of reaction resin and solidifying agent basically.Behind melt homogenization, this mixture have at least 40 ℃ Tg and usually under the situation of reactive polyurethane composition only more than 160 ℃ or under the situation of hyperergy polyurethane composition in reaction more than 100 ℃, generates the matrix that crosslinked urethane also forms this matrix material thus.This means that prepreg according to the present invention makes the back at it and be made of carrier and the reactive polyurethane composition as substrate material that applies (its with non-crosslinked but reactive form exist).
This prepreg so stable storing common a couple of days and even several weeks, and therefore can further be processed into matrix material at any time.Reactive and the not essential distinction of the bicomponent system of anti-storage that this is and has above described is because the latter begins reaction and crosslinked generation urethane immediately after spreading.
In the manufacturing of composite component, use prepreg according to the present invention based on the reactivity of the stable storing of fast light photograph or hyperergy polyurethane composition as transparent covering layer.This special transparent surface quality owing to the matrix-fiber that significantly improves than (in other words: extremely low fiber volume fraction) produce.Therefore it has relatively low fiber volume fraction.
For especially level and smooth transparent composite component surface, set＜50%, preferred＜40%, the fiber volume fraction of preferred＜35% especially.
Exemplarily show the manufacturing according to prepreg of the present invention among Fig. 1.
Show among Fig. 2 and have the same matrix material but an example of the manufacture method of the double-deck stable storing prepreg of different fiber volume fraction.
Can be by known devices and equipment by reaction injection moulding (RIM), reinforced reaction injection moulding (RRIM), pultrusion method, by in roll housing or by hot scraper, applying solution or other method is carried out according to the manufacturing of prepreg of the present invention.
Theme of the present invention particularly has the purposes of prepreg of the fibrous carrier of carbon fiber in addition.
Theme of the present invention also with good grounds prepreg of the present invention for the manufacture of the purposes of the composite component of the spinner blade of wind power generation plant (for example be used for) in the shipbuilding n., in the aeronautical and space technology, in the automobile making and in the preferred motorcycle of two wheeler and the bike and in building, engineering in medicine and motion, electricity and electronics industry and/or the parts at power generation assembly. [0085]Theme of the present invention also has the composite component of being made by prepreg manufactured according to the present invention, and the matrix material of wherein making (parts) has with employed fibrous carrier A) the surface of visible structure.
Embodiment
The reactive polyurethane composition
Has the reactive polyurethane composition of following prescription for the manufacture of prepreg and matrix material.
Figure 467724DEST_PATH_IMAGE002
The raw material of this table through pulverizing is mixed in premixed device closely, then in forcing machine in the highest 130 ℃ of following homogenizing.After this, this reactive polyurethane composition can be used for the manufacturing of prepreg according to manufacture method.This reactive polyurethane composition subsequently after grinding according to the powder impregnation method for the manufacture of prepreg.For direct melt impregnation method, can directly use the melted blend of the homogenizing of in forcing machine, making.
Dsc measurement
Carry out DSC research (second-order transition temperature is measured and reaction enthalpy is measured) with Mettler Toledo DSC 821e according to DIN 53765.
The second-order transition temperature that records extrudate is 61 ℃; Under fresh state, the reaction enthalpy of crosslinking reaction is 67.5 J/g.
After crosslinked (prepreg solidify, make laminating material), second-order transition temperature rises to 78 ℃ and no longer can detect crosslinked hot-fluid.
The manufacturing of prepreg
Implement the manufacturing of prepreg by means of direct melt impregnation method according to DE 102010029355.
The stability in storage of prepreg
Measure the stability in storage of prepreg with the reaction enthalpy of second-order transition temperature and crosslinking reaction by DSC research.
By at room temperature storing the crosslinked ability of not damaging this PU-prepreg 5 weeks.
Figure DEST_PATH_IMAGE003
Composite component is made
Make composite component at compound press by compact technique well known by persons skilled in the art.To be pressed into matrix material at bench press by means of the even prepreg that direct melt impregnation method is made.This bench press is Polystat 200 T from Schwabenthan company, with it prepreg is pressed into corresponding composite sheet under the temperature between 120 to 200 ℃.Pressure changes between normal pressure to 450 bar.According to part dimension ,-thickness and polyurethane composition and the therefore viscosity adjustment under processing temperature, dynamically compacting is namely alternately exerted pressure, and verifiedly is conducive to the wetting of fiber.
In an example, the press temperature is increased to 110 ℃ from 90 ℃ in melt stage, and pressure is increased to 450 bar after 3 minutes melt stage, and temperature continues to be increased to 140 ℃ during this period.Then temperature being risen to 180 ℃ also makes pressure remain on 350 bar until took out composite component from press after 30 minutes simultaneously.Test has a fiber volume fraction〉degree of cure (measuring by DSC) of 50% hard rigidity, chemicals-resistant and shock proof composite component (articles of sheet material).The crosslinked process of mensuration indication under different solidification values of the second-order transition temperature of the matrix through solidifying.In employed polyurethane composition, crosslinked fully after about 25 minutes, also no longer can detect the reaction enthalpy of crosslinking reaction then.

Claims (17)

1. have the prepreg less than 50% fiber volume fraction, it is following formation basically
A) at least a fibrous carrier that is constituted by carbon fiber
With
B) as at least a reactivity or the hyperergy transparent polyurethane composition of substrate material,
Wherein said polyurethane composition contains the polymkeric substance b with isocyanate-reactive functional group as tackiness agent basically) and as solidifying agent inside end-blocking a) and/or with the aliphatic series of end-capping reagent end-blocking, alicyclic and/or (ring) aliphatic series two-or the mixture of polyisocyanates.
2. according to the prepreg of claim 1,
Wherein said substrate material B) has at least 40 ℃ Tg.
3. according to the prepreg of at least one of aforementioned claim,
It is characterized in that,
Described prepreg have have employed carrier A) the surface of visible structure of carbon fiber.
4. according to the prepreg of at least one of aforementioned claim,
It is characterized in that,
Described fiber volume fraction＜50%, preferred＜40%, preferred＜35% especially.
5. according to the prepreg of at least one of aforementioned claim,
It is characterized in that,
Comprise the fabric of carbon fiber and grid cloth as carrier.
6. according to the prepreg of at least one of aforementioned claim,
It is characterized in that,
Use has the polymkeric substance b of hydroxyl, amino and thiol group), particularly having the OH value is that 20 to 500 milligrams of KOH/ grams and average molar mass are polyester, polyethers, polyacrylic ester, polycarbonate and the urethane of 250 to 6000 grams/mole.
7. according to the prepreg of at least one of aforementioned claim,
It is characterized in that,
That use is selected from is following two-or polyisocyanates as component starting compound a): isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), two isocyanato-dicyclohexyl methyl hydrides (H12MDI), 2-methylpentane vulcabond (MPDI), 2,2,4-trimethyl hexamethylene diisocyanate/2,4,4-trimethyl hexamethylene diisocyanate (TMDI) and/or norbornene alkyl diisocyanate (NBDI), preferred especially IPDI, HDI, TMDI and/or H 12MDI wherein also can use isocyanuric acid ester.
8. according to the prepreg of at least one of aforementioned claim,
It is characterized in that,
Use is selected from following outside end-capping reagent and is used for a) end-blocking: methyl aceto acetate, Diisopropylamine, methyl ethyl ketone oxime, diethyl malonate, ε-Ji Neixianan, 1,2,4-triazole, phenol or substituted phenol and/or 3.
9. according to the prepreg of at least one of aforementioned claim,
It is characterized in that,
Use contain isocyanurate group and ε-Ji Neixianan end-blocking the isocyanic ester structure the IPDI adducts as component a).
10. according to the prepreg of at least one of aforementioned claim,
It is characterized in that,
Described reactive polyurethane composition B) contain the other catalyzer of the amount of 0.001-1 weight %, be preferably dibutyl tin laurate, zinc octoate, neodecanoic acid bismuth, and/or tertiary amine, preferred 1,4-diazabicyclo [2.2.2] octane.
11. according to the prepreg of at least one of aforementioned claim,
It has derive from least a reactive polyurethane composition B that contains uretdion groups) substrate material, it contains basically
A) at least a solidifying agent that contains uretdion groups, described solidifying agent is based on the polyaddition compounds of the compound of the aliphatic or alicyclic polyisocyanates that contains uretdion groups of aliphatic series, (ring) and hydroxyl, wherein said solidifying agent exists with solid form below 40 ℃ and exists with liquid form more than 125 ℃, have less than the free NCO content of 5 weight % and the urea diketone content of 3-25 weight %
B) polymkeric substance of at least a hydroxyl, it exists with solid form below 40 ℃ and in the OH value that has and have 20 to 200 milligrams of KOH/ grams more than 125 ℃ with liquid form,
C) optional at least a catalyzer,
D) randomly, by polyurethane chemistry known auxiliary agent and additive,
So that these two kinds of components a) and b) exist with such ratio, namely in components b) each hydroxyl consume a) 0.3 to 1 of component, preferred 0.45 to 0.55 uretdion groups.
12. according to the prepreg of at least one of claim 1 to 9, it has at least a Powdered polyurethane composition B of hyperergy that contains uretdion groups) as substrate material, it contains basically
A) at least a solidifying agent that contains uretdion groups, it is based on aliphatic or alicyclic two of uretdion groups-or the polyisocyanates that contains of aliphatic series, (ring),
With
B) optional at least a polymkeric substance with NCO radical reaction functional group;
C) at least a catalyzer of 0.1 to 5 weight %, it is selected from halogen ion, hydroxide radical, alcoholate ion or organic or inorganic acid anion quaternary ammonium salt and/or the quaternary alkylphosphonium salt as counter ion;
With
D) at least a promotor of 0.1 to 5 weight %, it is selected from
D1) at least a epoxide
And/or
D2) at least a metal acetylacetonates and/or quaternary ammonium acetylacetonate and/or quaternary phosphine acetylacetonate;
E) randomly, by polyurethane chemistry known auxiliary agent and additive.
13. according to aforementioned claim 1 to 9 or 12 at least one s' prepreg, it has at least a Powdered polyurethane composition B of hyperergy that contains uretdion groups) as substrate material, it contains basically
A) at least a solidifying agent that contains uretdion groups, described solidifying agent is based on the polyaddition compounds of the compound of the aliphatic or alicyclic polyisocyanates that contains uretdion groups of aliphatic series, (ring) and hydroxyl, wherein said solidifying agent exists with solid form below 40 ℃ and exists with liquid form more than 125 ℃ and have less than the free NCO content of 5 weight % and the urea diketone content of 3-25 weight %
B) polymkeric substance of at least a hydroxyl, it exists with solid form below 40 ℃ and in the OH value that has and have 20 to 200 milligrams of KOH/ grams more than 125 ℃ with liquid form;
C) at least a catalyzer of 0.1 to 5 weight %, it is selected from halogen ion, hydroxide radical, alcoholate ion or organic or inorganic acid anion quaternary ammonium salt and/or the quaternary alkylphosphonium salt as counter ion;
With
D) at least a promotor of 0.1 to 5 weight %, it is selected from
D1) at least a epoxide
And/or
D2) at least a metal acetylacetonates and/or quaternary ammonium acetylacetonate and/or quaternary phosphine acetylacetonate;
E) randomly, by polyurethane chemistry known auxiliary agent and additive,
So that these two kinds of components a) and b) exist with such ratio, namely in components b) each hydroxyl consume a) 0.3 to 1 of component, preferred 0.6 to 0.9 uretdion groups.
14. according to the prepreg of at least one of aforementioned claim 1 to 13 purposes for the manufacture of matrix material, described prepreg especially has the fibrous carrier of carbon fiber-.
15. according to the prepreg of at least one of claim 1 to 14 for the manufacture of in the shipbuilding n., in the aeronautical and space technology, in the automobile making, be used for two wheeler, preferred motorcycle and bike, in automobile, building, medical technology and motion, electricity-and electronic industry, power station, for example purposes of the matrix material in the spinner blade field in the wind power plant.
16. according to the composite component of at least one of claim 1 to 13, it has the fiber volume fraction less than 50%.
17. according to the composite component of at least one of claim 1 to 13, the composite component of wherein making have have employed fibrous carrier A) the surface of visible structure.
CN2011800562520A 2010-09-23 2011-08-31 Prepregs based on a storage-stable reactive or highly reactive polyurethane composition Pending CN103210024A (en)

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US20130231017A1 (en) 2013-09-05
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